陈化体系中醇对Ce0.65Zr0.35O2及其负载的单Pd催化剂性能的影响

doi:10.15541/jim20140223

摘要/Abstract

摘要：

采用共沉淀法制备了Ce_0.65Zr_0.35O₂(CZ)储氧材料, 分别以乙醇-水、丙醇-水、乙二醇-水、丙三醇-水体系对沉淀物进行陈化, 研究了醇的种类对CZ及其负载的单Pd催化剂性能的影响。对CZ进行了扫描电镜(SEM), N₂-吸脱附分析, 对Pd/CZ进行了粉末X射线衍射(XRD)、X射线光电子能谱(XPS)、储氧量 (OSC)和程序升温还原( H₂-TPR)的表征, 并考察了三效催化性能。结果表明, 醇的种类对CZ及Pd/CZ的性能有显著影响。在乙醇-水和丙醇-水陈化体系中制备的CZ分散性高, 颗粒堆积松散, 比表面积和孔径大, 孔容高, 且具有优异的热稳定性, 其中丙醇-水陈化体系中制备的CZ老化后比表面积和孔容分别可达28 m²/g和0.1 mL/g, 具有最高的热稳定性, 其负载的单Pd催化剂在老化后对C₃H₈、CO和NO转化显著优于乙二醇-水和丙三醇-水陈化体系中制备的CZ所制备的催化剂。

关键词: 醇-水体系, CZ储氧材料, 单Pd催化剂, 性能

Abstract:

CZ oxygen storage material was prepared by co-precipitation method. The ethanol-water, propyl alcohol-water, ethylene glycol-water, and glycerol-water ageing systems were used to age the precipitate. CZ was characterized by scanning electron microscope (SEM) and nitrogen sorption techniques. Their corresponding Pd/CZ were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscope (XPS), oxygen storage capacity (OSC), and hydrogen temperature-programmed reduction (H₂-TPR) techniques. The results showed that the CZ prepared in ethanol-water and propyl alcohol-water ageing system exhibited large BET surface and pore size, high pore volume, as well as excellent thermal stability. The propyl alcohol-water imparted CZ the highest thermal stability, with BET surface of 28 m²/g and pore volume 0.1 mL/g after ageing. The corresponding aged Pd/CZ showed prominent catalytic performance. The T₅₀and T₉₀ of C₃H₈, CO and NO were lower than those over the catalysts prepared in ethylene glycol-water and glycerol-water ageing system obviously.

Key words: alcohol-water system, CZ oxygen storage material, Pd-only catalyst, performance

中图分类号:

O643

黄利华, 陈山虎, 龚茂初, 陈耀强. 陈化体系中醇对Ce_0.65Zr_0.35O₂及其负载的单Pd催化剂性能的影响[J]. 无机材料学报, 2015, 30(2): 195-201.

HUANG Li -Hua, CHEN Shan-Hu, GONG Mao-Chu, CHEN Yao-Qiang. Influence of Alcohol on Performance of Ce_0.65Zr_0.35O₂and Its Corresponding Pd-only Catalyst in Ageing System[J]. Journal of Inorganic Materials, 2015, 30(2): 195-201.

图/表 8

图 1 新鲜CZ的SEM照片

Fig. 1 SEM morphologies of fresh CZs (a) CZ-Y; (b) CZ-B; (c) CZ-YE; (d) CZ-BS

图 2 新鲜和老化CZ的吸脱附曲线图

Fig. 2 N2 adsorption/desorption isotherm of fresh and aged CZs

图 3 新鲜和老化CZ的孔径分布图

Fig. 3 Pore size distribution of fresh and aged CZs

图 4 新鲜和老化催化剂的XRD图谱

Fig. 4 XRD patterns of fresh and aged catalysts

图 5 新鲜和老化催化剂的Ce3d XPS图谱

Fig. 5 Ce3d XPS spectra of fresh and aged catalysts

表 1 新鲜和老化催化剂表面元素含量(%)

Table 1 Surface elemental composition (%) of fresh and aged catalysts

Catalyst	Fresh				Aged				Ce/Zr ratio		(u₃/Ce3d) /%
Catalyst	Ce3d	Zr3d	O1s	Pd3d	Ce3d	Zr3d	O1s	Pd3d	Fresh	Aged	Fresh	Aged
Pd/CZ-Y	16.29	8.99	73.24	1.49	11.86	9.11	78.10	0.93	1.81	1.30	16.52	17.02
Pd/CZ-B	14.13	8.06	76.02	1.25	11.81	9.18	78.06	0.95	1.75	1.29	16.38	16.43
Pd/CZ-YE	10.56	9.51	77.49	1.44	9.82	10.37	79.36	0.45	1.21	0.95	17.89	18.88
Pd/CZ-BS	9.63	8.39	80.28	1.70	8.95	10.58	79.79	0.68	1.15	0.85	18.22	18.64

图 6 新鲜和老化催化剂的H2-TPR图谱

Fig. 6 H2-TPR spectra of fresh and aged catalysts

表 2 新鲜和老化催化剂上C3H8、NO、CO的T50和T90

Table 2 T50 and T90 on fresh and aged catalysts

Catalyst		T₅₀/℃	T₉₀/℃
Catalyst		C₃H₈NO CO	C₃H₈NO CO
Fresh	Pd/CZ-Y	238 135 102	275 155 170
	Pd/CZ-B	243 132 110	280 150 180
	Pd/CZ-YE	270 175 150	310 195 210
	Pd/CZ-BS	290 185 160	330 205 235
Aged	Pd/CZ-Y	326 208 175	383 235 230
	Pd/CZ-B	318 192 165	370 210 215
	Pd/CZ-YE	395 275 260	- 320 300
	Pd/CZ-BS	380 265 250	420 305 295

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陈化体系中醇对Ce_0.65Zr_0.35O₂及其负载的单Pd催化剂性能的影响

Influence of Alcohol on Performance of Ce_0.65Zr_0.35O₂and Its Corresponding Pd-only Catalyst in Ageing System

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